Ion-Radical Organic Chemistry Principles and Applications Second Edition CRC_9068_FM.indd i 9/8/2008 12:18:29 PM CRC_9068_FM.indd ii 9/8/2008 12:18:30 PM Ion-Radical Organic Chemistry Principles and Applications Second Edition Zory Vlad Todres Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC_9068_FM.indd iii 9/8/2008 12:18:30 PM CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2009 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Printed in the United States of America on acid-free paper 10 International Standard Book Number-13: 978-0-8493-9068-5 (Hardcover) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the 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CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Library of Congress Cataloging-in-Publication Data Todres, Zory V., 1933Ion-radical organic chemistry: principles and applications / Zory Vlad Todres 2nd ed p cm Rev ed of: Organic ion radicals New York : Marcel Dekker, c2003 Includes bibliographical references and index ISBN 978-0-8493-9068-5 (alk paper) Radicals (Chemistry) Ions Organic compounds I Todres, Zory V., 1933- Organic ion radicals II Title QD476.T58 2008 547’.1224 dc22 2008022716 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com CRC_9068_FM.indd iv 9/8/2008 12:18:30 PM Dedication To my wife Irina: the cloudless beauty of her heart, profundity of her mind, and depth of her feelings in all times have always provided reliable support to me For my children, Vladimir and Ellen, their mother represents a superior, stimulating example CRC_9068_FM.indd v 9/8/2008 12:18:31 PM CRC_9068_FM.indd vi 9/8/2008 12:18:31 PM Contents Preface xiii Author xv Chapter Nature of Organic Ion-Radicals and Their Ground-State Electronic Structure 1.1 Introduction .1 1.2 Unusual Features .2 1.2.1 Substituent Effects 1.2.2 Connections between Ion-Radical Reactivity and Electronic Structure of Ion-Radical Products .7 1.2.3 Bridge-Effect Peculiarities 10 1.3 Acid–Base Properties of Organic Ion-Radicals 16 1.3.1 Anion-Radicals 16 1.3.1.1 Anion-Radical Basicity 16 1.3.1.2 Pathways of Hydrogen Detachment from Anion-Radicals 20 1.3.2 Cation-Radicals 22 1.3.2.1 Cation-Radical Acidity 22 1.3.2.2 Cation-Radical Basicity 29 1.3.2.3 Cation-Radicals as Acceptors or Donors of Hydrogen Atoms 30 1.4 Metallocomplex Ion-Radicals 30 1.4.1 Metallocomplex Anion-Radicals 30 1.4.2 Metallocomplex Cation-Radicals 33 1.4.3 Bridge Effect in Metallocomplex Ion-Radicals 36 1.4.4 Charge-Transfer Coordination to Metallocomplex Ion-Radicals 38 1.5 Organic Ion-Radicals with Several Unpaired Electrons or Charges 39 1.6 Polymeric Ion-Radicals 48 1.7 Inorganic Ion-Radicals in Reactions with Organic Substrates 53 1.7.1 Superoxide Ion 54 1.7.1.1 Reactions of Superoxide Ion with Organic H Acids 55 1.7.1.2 Reactions of Superoxide Ion with Organic Electrophiles 56 1.7.1.3 Reactions of Superoxide Ion with Biological Objects 57 1.7.1.4 Superoxide Ion–Ozone Anion-Radical Relation 57 1.7.2 Atomic Oxygen Anion-Radical 58 1.7.3 Molecular Oxygen Cation-Radical 58 1.7.4 Carbon Dioxide Anion-Radical 59 1.7.5 Carbonate Radical .60 1.7.6 Sulfur Dioxide Anion-Radical 61 1.7.7 Sulfite Radical 61 1.7.8 Sulfate Radical 62 1.7.9 Hydroxide Anion 65 1.7.10 Nitrosonium and Nitronium Ions 66 1.7.11 Tris(aryl)amine and Thianthrene Cation-Radicals 67 1.7.12 Trialkyloxonium Hexachloroantimonates 69 1.7.13 Transition Metal Ions 69 1.8 Conclusion 73 References 74 vii CRC_9068_FM.indd vii 9/8/2008 12:18:31 PM viii Chapter Contents Formation of Organic Ion-Radicals 85 2.1 Introduction 85 2.2 Chemical Methods of Organic Ion-Radical Preparation 86 2.2.1 Anion-Radicals 86 2.2.2 Cation-Radicals 89 2.2.3 Carbenoid Ion-Radicals .92 2.3 Equilibria in Liquid-Phase Electron-Transfer Reactions 93 2.4 Electrochemical Methods versus Chemical Methods 95 2.4.1 Charge-Transfer Phenomena .96 2.4.2 Template Effects 100 2.4.3 Adsorption Phenomena 103 2.4.4 Stereochemical Phenomena 106 2.4.5 Concentration Effects on the Fate of Ion-Radicals at Electrodes and in Solutions 110 2.4.6 Aggregation of Ion-Radical Salts 111 2.4.6.1 Direct Influence on Electron-Transfer Equilibrium 112 2.4.6.2 Electron-Transfer Reactions with Participation of Ion-Radical Aggregates 113 2.4.6.3 Kinetic and Mechanistic Differences between Electrode and Chemical (Homogeneous) Ion-Radical Dimerization 114 2.5 Formation of Organic Ion-Radicals in Living Organisms 115 2.6 Isotope-Containing Organic Compounds as Ion-Radical Precursors 117 2.6.1 Kinetic Isotope Effects in Electron-Transfer Reactions 118 2.6.2 Behavior of Isotope Mixtures in Electron-Transfer Reactions 120 2.7 Organic Ion-Radicals in Solid Phases 126 2.7.1 Organic Ion-Radicals in Frozen Solutions 126 2.7.2 Organic Ion-Radical as Constituents of Solid Salts 130 2.8 Formation and Behavior of Ion-Radicals within Confines 130 2.8.1 Micellar Media 130 2.8.2 Porous Media 131 2.8.3 Capsule Media 133 2.9 Conclusion 135 References 136 Chapter Electronic Structure–Reactivity Relationship in Ion-Radical Organic Chemistry 143 3.1 Introduction 143 3.2 Principle of “Detained” Electron That Controls Ion-Radical Reactivity 144 3.2.1 Frontier-Orbital Control 144 3.2.2 Steric Control over Spin Delocalization 153 3.2.3 Unpaired Electron Localization in the Field of Two or More Atoms 155 3.2.4 Spin–Charge Separation (Distonic Stabilization of Ion-Radicals) 161 3.2.4.1 Distonic Stabilization of Anion-Radicals 163 3.2.4.2 Distonic Stabilization of Cation-Radicals 165 3.2.5 Ion-Pair Formation 168 3.2.5.1 Detention of Unpaired Electron in a Framework of One Specific Molecular Fragment 169 3.2.5.2 Formation of Closed Contour for Unpaired Electron Delocalization 170 CRC_9068_FM.indd viii 9/8/2008 12:18:31 PM Contents ix 3.3 Principle of “Released” Electron That Controls Ion-Radical Reactivity 178 3.3.1 Effects of Spread Conjugation in Ion-Radicals Derived from Molecules with Large Contours of Delocalization 180 3.3.2 Spin Delocalization in Ion-Radicals Derived from Molecules of Increased Dimensionality 183 3.4 Biomedical Aspects of Ion-Radical Organic Chemistry 186 3.4.1 Cation-Radical Damage in Deoxyribonucleic Acid 186 3.4.1.1 Ionization Potentials of Carcinogens 187 3.4.1.2 Localization of Charges and Spins in Cation-Radicals of Carcinogens 187 3.4.2 On Geometrical and Spatial Factors Governing the Behavior of Ion-Radicals in Biological Systems 189 3.4.3 Ion-Radical Repair of Damaged Deoxyribonucleic Acid 191 3.4.4 Cation-Radical Intermediates in Metabolism of Furan Xenobiotics 194 3.4.5 Behavior of Anion-Radicals in Living Organisms 194 3.5 Conclusion 196 References 197 Chapter Discerning Mechanism of Ion-Radical Organic Reactions .205 4.1 Introduction 205 4.2 Why Do Reactions Choose Ion-Radical Mechanism? 205 4.3 Chemical Approaches to Identification of Ion-Radical Organic Reactions 209 4.3.1 Identification According to Structure of Final Products 209 4.3.2 Identification According to Correlation within Reaction Series 213 4.3.3 Identification According to Disturbance of “Leaving-Group Strength” Correlation 215 4.3.4 Kinetic Approaches to Identification of Ion-Radical Reactions 216 4.3.4.1 Kinetic Isotope Effect 216 4.3.4.2 Other Kinetic Approaches 217 4.3.5 Positional Reactivity and Distribution of Spin Density in Substrate Ion-Radicals 219 4.3.6 Identification by Methods of Chemical Probes 223 4.3.6.1 Initiation of Polymerization of Vinyl Additives 223 4.3.6.2 Method of Inhibitors 224 4.3.6.3 Method of Radical and Spin Traps 227 4.4 Physical Approaches to Identification of Ion-Radical Reactions 232 4.4.1 Radiospectroscopy 232 4.4.1.1 Electron Spin Resonance Methods 232 4.4.1.2 Nuclear Magnetic Resonance Methods 233 4.4.2 Optical Spectroscopy Methods 236 4.4.2.1 Electron Spectroscopy 236 4.4.2.2 Vibration Spectroscopy 238 4.4.3 Other Physical Methods 238 4.4.3.1 Magnetic Susceptibility 238 4.4.3.2 Mass Spectrometry 238 4.4.3.3 Electrochemical Modeling of Ion-Radical Reactions 238 4.4.3.4 X-Ray Diffraction 239 4.5 Examples of Complex Approaches to Discernment of Ion-Radical Mechanism of Organic Reactions 240 4.5.1 Oxidative Polymerization of Anilines .240 4.5.2 Reactions of Hydroperoxides with Phosphites and Sulfides 241 CRC_9068_FM.indd ix 9/8/2008 12:18:31 PM Author Index Rusanov, A.L., 284 Russell, G.A., 210, 216, 280, 293, 332, 356, 394 Russo, C.C., 27 Rutavichus, A.I., 109 Ruzziconi, R., 386 Ryabinin, V.A., 292 Ryabkina, L.V., 27 Ryan, M.D., 158 Rybakova, I.A., 215 Rybarczyk-Pirek, A., 37 Rykova, L.A., 217 Ryzhakov, A.V., 151 Ryzhova, G.L., 170 S Saafeld, F., 194 Saalfrank, R.W., 415 Sa’ar, A., 240 Sabino, A.A., 167, 248, 260, 261 Sachdeva, Ye.P., 223 Sacher, M., 178 Sada, N., 51 Sadakata, M., 58 Sadek, H., 168 Saeki, A., 53 Saeki, K., 373 Saeki, M., 59 Saettel, N.J., 193, 323 Saeva, F.D., 105, 145, 208 Safadi, A., 194 Safiullin, R.L., 63 Safronov, A.I., 34, 147, 337 Sagae, H., 293 Sagdeev, R.Z., 277 Sage, M.A., 110 Sahin, C., 378 Sahin, Y., 10 Saidi, M.R., 384 Saito, G., 410, 413, 414 Saito, K., 237, 238 Saito, Y., 415 Sakae, T., 312 Sakai, K., 379 Sakaki, D., 119 Sakamoto, A., 238 Sakamoto, M., 274 Sakata, M., 358 Sakata, Y., 415 Sakurai, H., 41 Salamone, M., 25 Salahub, D.R., 29 Salhi-Benachenhou, N., 343 Salikhov, K.M., 277 Salman, H.M.A., 38 Saluvere, T.A., 235 Salzman, Ch., 37 Samachetty, H.D., 404 Samajdar, S., 257 Samal, S., 135 Samoilova, R., 300 CRC_9068_authorind.indd 463 463 Sanaeva, E.P., 27 Sanche, L., 58 Sandall, J.P.B., 249, 252 Sanderson, C.T., 358 Sandona, G., 17 Sandra, E., 60 Sang, H., 228, 242 Sangari, S.S., 286 Sankararaman, S., 257, 311, 367, 368 Santalo, N., 411 Santhanam, K.S.V., 178 Santiago, A.N., 272, 394 Santiago, G., 89 Santoh, T., 407, 408 Santos Veiga dos, J., 173 Sanyal, A., 89 Sapunov, V.N., 379 Sapurina, I.Yu., 113 Sarkanen, S., 24 Sarkar, B., 10 Sarker, H., 360, 361, 387 Sartillo-Piscil, F., 330 Sartor, V., 193 Sasai, Y., 285, 286 Sasaki, D., 119 Sasaki, Sh., 13, 14 Sasamory, T., 14 Sastry, N., 118 Sasz, G., 332 Sato, K., 14, 43–45, 232, 298 Sato, R., 34, 73 Sauer, M.C., 60, 305 Saunders, R., 194 Sauvage, J.-P., 31, 443 Savall, B.M., 416 Saveant, J.-M., 7, 27, 33, 54, 60, 94, 96, 105, 144, 196, 207, 208, 216, 274, 276, 299, 302, 303, 385, 392, 397, 398 Savin, A., 156 Sawamura, M., 19 Sawyer, D.T., 54–56, 59, 65, 66 Schaefer, H.F., 97, 193, 365, 358 Schaefer, H.J., 97 Schank, K., 57 Schanze, K.S., 41, 386 Schauer, C.K., Scheidt, J., 193 Scheidt, W.R., 33, 239 Scheloske, M., 301 Schelter, J., 10, 297 Scenetti, L., 336 Schenk, R., 174 Schepp, N.P., 24, 298 Schertz, T., 89 Schertz, T.D., 297 Schiesser, C.H., 375 Schlag, E.W., 193 Schlegel, H.B., 329 Schlesener, S.J., 118 Schlueter, K., 185 Schmalz, Th.G., 190 Schmebzer, A., 343 Schmidlin, R., 115 Schmidt, I., 125 Schmidt, K., 305 Schmidt, L.C., 316 Schmidt, U., 382 Schmidt-Naake, G., 285 Schmitt, M., 10 Schmitt, R.J., 261 Schmittel, M., 22, 337 349, 385 Schmusser, W., 332 Schmuttenmaer, C.A., 181 Schnabel, E., 382 Schneider, K.-A., 343, 344 Schneider, R., 184, 332 Schnering von, H.-G., 138, 417 Schoemaker, H.E., 378, 429 Schoen, J., 117 Schoeneich, Ch., 158, 160, 161 Schoffield, K., 248 Scholtz, M., 94, 156 Schottenberger, H., 35 Schroth, W., 335 Schryver de, F.C., 52 Schuchmann, M.N., 59 Schuddeboom, W., 306 Schuetz von, J.U., 417 Schulbert, L., 90 Schulz, A., 92 Schultz, T.P., 433 Schumaker, R.R., 412 Schumer, F., 335 Schuster, G.B., 193 Schutz, O., 60 Schwan, A.L., 146 Schwartz, R.L., 58 Schwarz, H., 158 Schwartz, W., 427 Schweiger, A., 161 Schwogler, A., 192 Schwerdski, B., 10 Scott, J.C., 417 Screenath, K., 357 Screttas, C.G., 19, 20, 233, 395 Scurrell, M.S., 240, 241 Sebastiani, G.V., 386 Seddon, K.R., 307 Sedlacek, J., 37 Seebach von, M., 9, 127, 232 Seeber, R., 336 Sehested, K., 22, 58 Sehgal, C., 87 Seidel, D., 103 Sekher, P., 155 Seki, K., 413 Seki, Sh., 52, 53 Sekiguchi, A., 92, 162, 163 Sekuguchi, M., 153 Selby, T.D., 43, 50 Seledets, M., 360 Selinka, C., 297 Selivanova, G.A., Selman, J.R., 406 Selvapalam, N., 135 9/4/2008 11:45:49 AM 464 Selwood, P., 238 Senba, N., 419 Sengupta, S., 31 Senkal, B.F., 50 Senna, M., 135 Seo, E.T., 90 Seok, S.-J., 227 Sergeev, S.V., 97 Serikov, T.P., 434 Serita, M., 157 Serpa, C., 303 Serve, D., 53 Servy, C., 259 Sessions, R.B., 156, 157 Sessler, J.L., 103 Setchel, F., 191 Sevast’yanov, V.G., 15, 98 Sevenster, A.J.L., 333 Sevila, M.D., 26 Shabel’nikov, V.P., 68 Shacklette, L.W., 331 Shaefer, C.G., 310 Shafer, Sh.J., 222 Shah, B., 229 Shah, Sh., 14, 156 Shaik, S., 118, 329 Shakirov, M.M., 255, 256 Shames, A., 297 Shamsutdinova, M.Kh., Shao, J., 33 Shapiro, B.I., 245, 247 Shapiro, L., 297 Shatenshtein, A.I., 86 Shatnawi, M., 131 Shaw, M.J., 91, 338 Shchapin, I.Yu., 29 Shchegoleva, L.N., 2, 232 Shchegolikhin, A.N., 27 Shealer, S.E., 362 Sheasby, J.S., 427 Shechter, H., 246 Shein, S.M., 65, 66, 218, 224, 225, 292 Sheka, I.A., 72 Sheka, M.A., 72 Shekhtman, R.I., 215 Sheldon, R.A., 379 Shen, J., 2, 261 Shereshovets, V.V., 90 Sherrington, D.C., 352 Shevelyov, S.A., 257 Shi, B., 125 Shi, Y.Z., 87 Shibaeva, R.P., 410, 414 Shida, T., 128, 185 Shields, T.M., 273 Shigemitsu, Y., 362 Shigetomi, Y., 273 Shih, S., 71, 221 Shihab, M.S., 304 Shiihasi, S., 66 Shilov, A.E., 151 Shim, Y., 363 CRC_9068_authorind.indd 464 Author Index Shimamori, H., 303 Shimizu, C., 36 Shimizu, M., 119, 415 Shimizu, Y., 148 Shine, H.J., 133, 187, 290 Shingu, H., 149 Shinkar’, E.V., 30 Shinohara, H., 358 Shinomura, E.T., 33, 233 Shintani, F., 259 Shioji, K., 12 Shiomi, D., 14, 43, 45, 232, 298 Shiotani, M., 29, 127, 129 231, 332 Shirakura, S., 358 Shiratori, Y., 157 Shirota, H., 301 Shirota, Y., 43 Shishkov, A.V., 126 Shishlov, N.M., 90 Shiwaku, K., 416 Shklover, V.E., 38, 96 Shkrob, I.A., 60, 305 Shono, T., 291 Shoute, L.C.T., 191 Shpakov, A.I., 385 Shteiman, V.Ya., 251 Shteingarts, V.D., 2, 8, 18, 233, 356 Shternshis, M.V., 225 Shubin, V.G., 255, 256 Shugalei, I.V., 57, 243, 245–247 Shultz, D.A., 41 Shundrin, L.A., Shut, D.M., 31 Sibert, J.W., 327 Sidorenkova, H., 13, 14 Sidot, Ch., 395 Siedle, A.R., 415 Siedschlag, C., 30 Siegbahn, P.E.M., 191 Sieiro, C., 170, 171 Sies, H., 57 Sievert, M., 89 Sigwalt, P., 358 Sikora, A., 116, 385 Silva, K., 286 Simic, M., 58 Simig, G., 176, 226 Simkin, M.V., 442 Simon, J.D., 12, 310, 312 Simon, P., 230 Simonescu, C.I., 284 Simonet, J., 9, 277, 310, 335, 369, 373 Simonov, S.V., 410, 414 Simons, R.S., 163 Sindelar, V., 135 Singer, L.S., 91 Singh, A., 130 Singh, B.C., 427 Singh, H.K., Singh, P.R., 4, 209, 215, 223–225 Singh, S.P., 251 Singh, P., 98 Singleton, D.A., 366 Sinisterra-Gago, J.V., 280 Sinnecker, S., 300 Sinoharaha, H., 358 Sintic, P.J., 33 Siraki, A.G., 229 Skabara, P.J., 38 Skancke, P.N., 176 Skibar, W., 37 Skogareva, L.S., 62 Skokov, S., 253 Skolozdra, O.M., 360 Skrzypczak, A., 307 Skuratova, S.I., 65 Slovokhotova, N.A., 29 Small, D.W., 302 Smela, E., 52 Smertenko, E.A., 195 Smid, J., 306 Smirnov, A.I., 123, 159 Smit, C.J., 308 Smith, C.W., 382 Smith, D.K., 302, 406 Smith, G.P., 91 Smith, H., 427 Smith, H.O., 20 Smith, K., 256 Smith, P.H.G., 374, 395 Smith, R.C., 14 Smith, W.H., 120 Smith-King, R.J., 324 Smorodov, E.A., 280 Snelgrove, D.W., 328 Snow, D.H., 291 Snow, L.D., 129 Snyder, S.H., 131 Soames, P.W., 221 Sobransingh, D., 135 Sodupe, M., 165 Sohma, J., 231 Sokolov, V.I., 90 Sola, M., 148 Solodovnikov, S.P., 8, 86 Solooki, D., 372 Somekawa, K., 185 Sonnntag von, C., 59 Soo, L., 278 Soos, Z.G., 92 Sorbransingh, D., 135 Sosonkin, I.M., 94, 230 Sotiriou-Leventis, Ch., Sotnikova, N.N., 175 Souma, Y., 253–255 Soumillion, J.P., 273 Sourisseau, C., 90 Spagnolo, P., 387 Sparrapan, R., 167, 248, 260, 261 Speiser, B., 208, 387 Spitzner, R., 335 Spoyalov, A.P., 300 Spreti, S., 273, 386 Squadrito, G.L., 259 Squella, J.A., 195 9/4/2008 11:45:49 AM Author Index Squires, R.R., 164, 165 Srdanov, G., 20 Srdanov, V.I., 20 Srebotnik, E., 431 Sreenath, K., 105, 106, 179 Srinivasan, N., 307 Sriniwasan, S., 229 Staab, H.A., 10–12, 91 Stack, D.E., 187 Staedel, W., 172 Stagko, A., 156 Stahl, G.L., 382 Stahl, H., 387 Stahl, R., 10 Staley, S.W., 43, 300 Stalke, D., 10, 297 Stamboliyska, B.A., 333 Stamirez, D.N., 91 Staninets, V.I., 195 Stankevich, I.V., 8, 9, 354 Starichenko, V.F., 2, 4, Starodub, V.A., 418 Startsev, A.N., 434 Stass, D.V., 22, 232 Stasko, A., 90 Statsyuk, V.N., 72 Steckhan, E., 96, 97, 364–366, 383 Steele, B.R., 233 Steenken, S., 386, 434 Steinfatt, I., 104 Stemp, E.D.A., 193 Stender, M., 163 Stengel, P.J., 378 Stenman, D., 61 Stenzel, T.T., 276, 277 Stephens, P.W., 359 Stepien, M., 103 Stepnicka, P., 37 Stevenson, Ch.D., 21, 41, 88, 89, 120–125, 168, 175, 297, 300, 310, 354, 355, 387 Stevenson, G.R., 121, 119, 21, 124 Stevenson, J.P., 163 Stevenson, R.D., 121, 123 Stewart, J.J.P., 256 Stickley, K.R., 43, 50 Stienlet, D., 29 Still, I.W.J., 104 Stinchcombe, J., 237 Stipa, P., 229 Stock, L.M., 434 Stone, E.W., 2, 3, 334 Stone, T.J., Stowasser, R., 57 Strachan, E., 25 Stradins, J., 22 Stradowski, C., 156 Strasser, Ch.E., 35 Streitwieser, A., 15 Stringfellow, Th.C., 47 Stringle, D.L.B., 146, 195 Strizhakova, N.G., 72 Strnad, J.T., 43 CRC_9068_authorind.indd 465 465 Strogov, G.N., 230 Strom, B.D., 427 Struchkov, Yu.T., 38, 96, 97, 101, 177, 425 Stuart, J.D., 96 Stuchal, F.W., 286, 287 Studler-Martinez, Sh.L., 12 Sturgeon, B.E., 121, 124 Su, Zh., Subba Rao, U.V., 51 Subramaniam, G., 155 Subramanian, J., 333 Suchanski, M.R., 415 Sudhakar, P.V., 12 Sudmale, I., 417 Suenaga, K., 358 Suenaga, Y., 416 Suenobu, T., 370 Suga, M., 91 Sugata, Y., 407, 408 Sugawara, T., 41, 424 Sugimoto, T., 416 Suhr, H., 215 Suk, D.-H., 92, 185, 330 Sukhov, F.F., 29 Sulek, M.W., 425 Suleman, N.K., Sullivan, A.T., 144, 145 Sullivan, B.P., 314 Sullivan, P.D., 91 Sumegi, L., 230 Sumida, J.P., 306 Sun, Ch.-Ch., 86 Sun, D., 44, 155 Sun, F., 404 Sun, H.-B., 257 Sun, M., 331 Sun, Y., 240 Sundaresan, T., 171 Sung, J., 341 Surin, N.G., 354 Surya Prakash, G.K., 247 Surzur, J.-M., 223 Suslick, K.S., 280 Sutherland, K.N., 340 Sutherland, R.G., 87 Sutin, N., 213 Suzuki, H., 259, 326 Suzuki, T., 417 Suzuki, Y.J., 194 Svanholm, U., 96, 289, 290 Svendsen, Ch., 335 Svetkin, Yu.N., 70 Sviridenko, F.B., 22, 232 Svith, H., 298 Swanson, D.D., 158 Swartz, J.E., 276, 277 Swavey, Sh., 156 Swec, W.A., 405 Swiger, R.T., 286, 287, 291 Symons, M.C.R., 90, 129, 192 Syrkin, Ya.K., 245, 247 Szabo, C., 259 Szabo, D., Szajerski, P., 386 Szczepura, L.F., 41, 159 Szeghalmi, A.V., 10 Szepes, L., Szwarc, M., 112, 306 Szyczewski, A., 30 T Tabakovic, I., 298 Tabner, B.J., 20, 333 Tabohashi, K., 379 Tachikawa, H., 53, 332 Tachikawa, T., 133 Tachiya, M., 302 Tackley, D.R., 339 Tada, M., 63 Tada, T., 416 Taddei, F., 104, 425 Tagawa, S., 52, 53 Tagesson, B., 53, 70 Tagowska, M., 240 Takabe, T., 261 Takada, R., 52 Takagi, N., 14, 163 Takahashi, H., 65, 359 Takahashi, I., 50 Takahashi, K., 175 Takahashi, O., 387 Takahashi, T., 304 Takahashi, Y., 379 Takai, M., 359 Takamuku, S., 118 Takaoka, K., Takata, M., 358 Takata, T., 57 Takeda, N., 128 Takeda, S., 419 Takemura, Y., 185 Takenaka, K., 261 Takimiya, K., 412 Takiyama, K., 413 Takui, T., 14, 43–45, 232, 298 Talham, D.R., 36 Tallec, A., 207, 208, 303, 405 Tamaoki, M., 157 Tamura, R., 289, 392 Tan, J., 259 Tan, Y.-M., 307 Tanaka, A., 178 Tanaka, H., 358 Tanaka, J., 261, 415 Tanaka, K., 42, 43, 180, 288 Tanaka, M., 253–255, 415 Tanaka, Y., 49 Tang, R.T., 91 Tang, T.B., 413 Tang, T.-H., 380 Tang, X., 240 Tani, T., 108 Tanigaki, K., 359 9/4/2008 11:45:49 AM 466 Taniguchi, A., 178 Taniguchi, M., 419 Tanino, N., 336 Tanko, J.M., 25, 122, 163, 362 Tantillo, D.J., 183, 344 Tanzella, F.L., 59 Tao, Y., 114 Tarabek, P., 26 Tardivel, R., 207, 208, 303 Tardy, C., 1, 207, 208, 303 Tarnopolsky, A., 107 Tarraga, A., 37 Tarres, J., 411 Tasumi, M., 238 Tatemitsu, H., 415 Tatsumi, K., 115 Tatsumi, M., 44 Tatsumi, Y., 303 Taube, H., 351 Tauber, M.J., 406 Taylor, E.C., 90 Taylor, N., 43, 48, 51 Tazuke, S., 314 Tegze, M., 359 Teillout, A.-L., 302 Tejero, I., 218 Teki, Y., 340 Telo, J.P., 4, 12, 58, 63, 178, 297, 331, 334 Teng, X., 374, 375 Terabe, S., 229 Terada, E., 45 Terazima, M., 130, 255, 304 Teregulova, A.N., 63 Terekhova, M.I., 88 Terme, T., 392 Terron, G., 14 Tessier, C.A., 372 Testaferi, L., 6, 146, 207 Teunissen, P.J.M., 429 Thamiongkit, P., 125 Theiss, T.E., 251 Themans, B., 331 Theophilou, N., 240 Thiebault, A., 208, 216, 274 Thiel, F.A., 41 Thiele, J., 171 Thomas, C.B., 91 Thomas, B., 63 Thommen, W., 16, 353 Thompson, J.D., 420, 422 Thompson, M.E., 406 Thompson, N.J., 42 Thompson, P.A., 312 Thorp, H.H., 19 Thouin, L., 38 Tian, Y., 34 Tibbels, S.R., 187, 190 Tidwell, Th.T., 161 Tiecco, M., 6, 146, 207, 300, 335 Tien, M., 429, 432, 433 Tiernan, Ch., 176 Tierney, J., 279 CRC_9068_authorind.indd 466 Author Index Tilborg van, W.J., 308 Tilika, V., 417 Timerghazin, Q.K., 90 Timmel, Ch.R., 277 Timoshok, A.V., 63 Tingoli, M., 6, 146, 300 Tipkin, D.S., 280 Titov, V.E., 68 Titova, I.A., 150 Tobe, M., 235 Tobler, L., 260 Todres, Z.V., 3–5, 8, 9, 12, 14, 15, 18, 31, 34, 70, 93, 96–101, 104, 105, 107, 09, 112 , 129, 146, 147, 154 169, 170, 176, 177, 209, 227, 237, 247, 248, 257, 262, 263, 281, 282, 323, 325, 337, 403, 425 Toganoh, M., 19 Tohma, H., 368 Tojo, S., 12, 133 Tokieda, N., 151 Tokitoh, N., 14, 118 Tokuda, Y., 385 Tolksdorf, Ch., 443 Tomalla, M., 255 Tomazella, D.M., 167 Tomer, K.B., 187, 190 Tomilin, O.B., 9, 27, 354 Tominaga, T., 130, 255 Tomioka, H., 98 Tomkins, R.P.T., 296 Tomura, M., 411 Tonoi, T., 280 Toppare, L., 326 Tordeux, M., 183, 184, 332, 396 Tordo, P., 12, 229 Torii, H., 238, 413 Torimoto, Y., 58 Toriyama, K., 29 Torrelles, X., 153 Torsell, K., 228, 253 Toshima, T., 51 Toshimasa, M., 426 Tossel, J.A., 185 Townsend, J., 178 Toyota, N., 416 Traber, R.P., 222 Tran, H.Q., 340 Trapp, Ch., Tremelling, M.J., 216 Trenkle, H., 337 Trieiber, D.A., 68, 340 Trifonova, G.V., 262 Trifunac, A.D., 185, 232, 233, 305 Trinajstic, N., 182 Trindle, C., 380 Trofimov, A.V., 304, 344 Trogolo, C., 331 Troisi, A., 301 Trout, N.A., 392 Troxler, H., 94, 156 Truong, D., 302, 406 Truscott, T.G., 16, 59 Truttmann, L., 115 Tryk, D.A., 239 Tsai, Y.-C., 279 Tsang, E.M.W., 35, 37 Tsang, P.K.S., 65 Tsay, Sh.-Ch., 382 Tschumper, G.S., Tselinskii, I.V., 57, 243, 245–247 Tsenov, J.A., 147 Tsiperman, E., 297 Tsuchida, E., 47 Tsuchiya, M., 194 Tsukuda, T., 59 Tsuno, Y., 119, 122 Tsunoda, S., 406 Tsurusaki, A., 14 Tsutsumi, H., 240 Tsutsumi, Sh., 108 Tsveniashvili, V.S., Tsvetkova, T.M., 15, 98, 146 Tsyryapkin, V.A., 107 Tu, J., 58 Tu, T., 383 Tuccio, B., 229 Tucker, J.H.R., 302, 406 Tudos, F., 230 Tuemmler, R., 427 Tukada, H., 181 Tung, C.H., 404 Turaeva, D.A., 150 Turecek, F., 165 Turk, M.R., 168 Turkevich, J., 91 Turner, G.M., 181 Turner, S.S., 422 Turro, N.J., 133 Twardowski, A., 50 Tycko, R., 416 Tyler, D.R., 31 Tyryshkin, A.M., 300 Tyurin, D.A., 157 Tyutyulkov, N., 181 U Uchida, I., 406 Uchida, T., 183 Ueda, K., 98, 417 Ueda, N., 151 Uedo, K., 416 Uehata, A., 316 Ueno, Yu., 238 Ufimtsev, V.N., 251 Ulrich, V., 196 Ulyukina, E.A., 29 Umeda, M., 406 Umemoto, K., 221 Uno, B., 237 Urabe, M., 180 Uranga, J.G., 394 Urbach, B., 240 Urbach, F.L., 156 9/4/2008 11:45:50 AM Author Index Urban, Ch., 31 Urbin, S.A., 131 Urbina, J.A., 116 Uriuchi, M., 411 Urry, G.W., 21 Ustynyuk, N.A., 98 Utley, H.P., 326 Utley, J.H.P., 20 Utz, R., 382 V Vaccaro, L., 369 Vafina, A.A., 175 Vaillard, S.E., 373, 392 Vairamani, M., 213 Vakul’skaya, T.I., 150 Valenzuela, J., 10, 11 Valgimigli, L., 92 Valverde-Aguilar, G., 340 Van Aken, B., 431 Van Asselt, R., 102 Van Caemelbecke, E., 358 Van Duyne, R.P., 415 Van de Vorst, A., 191 Vanderah, T.A., 415 Vanderzande, D., 102 Vanelle, P., 279, 392 Vanherck, J.-Ch., 383 Vank, J.C., 380 Vargas, M., 330 Varghese, B., 367, 368 Vasin, V.A., 167 Vasquez-Vivar, J., 229 Vass, G., Vaultier, M., 307, 308 Vazquez, C., 183, 420 Veciama, J., 35, 37, 148, 182, 411 Vekey, K., 226 Velasco, D., 335 Velasco, M.D., 37 Velavan, K., 213 Velayutham, M., 229 Venkataramanan, N.S., 213 Venepalli, B., 86 Venturi, M., 443 Vera, D.M.A., 394 Verhoeven, J.W., 306 Verkhozina, O.N., 150 Vermeer, P., 185 Verrall, R.E., 87 Vessieres, A., 38 Vetoshkina, L.V., 417 Vezin, H., 132, 133 Viale, A., 33 Vianello, E., 93 Vicens, J., 443 Vidal-Gancedo, J., 37, 148, 182, 423 Vieira, A.J.S.C., 26, 68, 62, 63, 178 Vigante, B., 22 Viglione, R., 36 Viladoms, P., 373 CRC_9068_authorind.indd 467 467 Vilar, H., 207 Vilchevskaya, V.D., 38 Villamena, F.A., 229 Vinatoru, M., 281, 283 Vines, K.Sh., 124 Vinogradov, M.G., 109 Viruela, P.M., 52 Vishnetskaya, M.V., 28 Vivekananda, S., 165 Vlceck, A.A., 31 Vogel, E., 30 Vogte, M., 161 Vohlidal, J., 37 Voit, B., 156 Voityuk, A.A., 192 Vokin, A.I., 150 Volanschi, E., 146, 369 Volger, C., 31 Volkov, V.A., 150 Volodin, A.M., 63 Vol’pin, M.E., 70 Voorst van, J.D.W., 228 Vorbrueggen, H., 382 Voronenkov, V.V., 379 Vos, A., 16 Voss, J., 332 Vostrikova, L.A., 256 Voth, G.A., 302 Vuolle, M., 336 Vyazankin, N.S., 395 Vysotsky, V.P., 232 V’yushkova, M.M., 232 W Wacher, P., 359 Wada, Y., 373 Waelchli, M., 358 Wagner, Ch., 57 Wagner, E.P., 121 Wagner, K., 382 Wagner, M., 50 Wagnerova, D.A., 57 Wajer, A.J.W., 228 Wakabayashi, T., 65 Wakahara, T., 358 Wakamatsu, K., 273 Wakamiya, A., 167, 336 Wakasa, M., 278 Wake, R.W., 167 Wakselman, C., 396 Walcarius, A., 184, 332 Waldek, D.H., 154 Walker, G.C., 306 Walker, K.A., 34 Wall, S.T., 314 Wallis, J.D., 415 Wallwork, S., 107, 171 Walmsley, R.G., 427 Walree van, C.A., 306 Walter, R., 67, 382 Walton, G., 212 Waltz, W.L., 60 Wang, Ch., 306 Wang, H.B., 24 Wang, H.H., 416 Wang, J.T., 8, 129, 362 Wang, L., 58 Wang, L.H., 133, 194 Wang, L.X., 87 Wang, P.A., 354, 356 Wang, R., 135, 176 Wang, S.C., 183, 344 Wang, X., 131, 340 Wang, X.-L., 24 Wang, Y., 34, 55, 272 Wanner, M., 31 Ward, L., 13 Ward, M.D., 183, 417, 443 Ward, P., 91, 154 Ward, R.L., 176 Wardman, P., 115 Warford, E.W.T., 248 Warman, J.M., 301, 306 Warnek, P., 260 Warner, C.D., 187, 190 Wartel, M., 53, 67, 250, 258 Wartini, A., 10, 11 Warzecha, K-D., 325 Wasielewski, M.R., 405, 406 Wasserman, E., 183 Wasserman, H.H., 388 Watanabe, H., 135 Watanabe, K., 148 Watanabe, T., 190 Watanabe, Y., 14 Waters, W.A., 3, 262 Wathey, B., 279 Wawzonek, S., 114 Wayner, D.D.M., 25, 27, 298, 433 Weaver, M.N., 4, 262, 285, 297, 331, 334 Weber, W.P., 406 Webster, R.D., 24 Weddle, C.C., 196 Wehrmann, G.C., 121 Wei, D., 241 Wei, L., 157 Wei, Y., 240 Weinberg, H.R., 106 Weinberg, N.L., 105, 106 Weiner, L., 35, 356 Weinkauf, R., 193 Weinstock, I.A., 170 Weisman, G.R., 339 Weiss, J., 90, 159 Weissmann, S.T., 90, 178 Weitz, E.Z., Welp, U., 416 Welton, J.A., 307 Welton, T., 279 Welvart, Z., 183, 184, 299, 328, 332 Wen, X.-L., 122, 124 Weng, H., 28 Wenthold, P.G., 164 9/4/2008 11:45:50 AM 468 Werner, H.P., 417 Werst, D.W., 24, 185, 232, 303, 304 Wesdemiotis, Ch., 166 West, A.P., 101 West, P.R., 176 West, R., 47, 336 Westman, J., 279 Weston, S.C., 410, 411, 413 Westwood, J., 302, 406 Weyhensmeyer, J.A., 67 Wheeler, R.A., 253 Whitaker, R.G., 240 White, A.C., 68 White, C., 338 White, H.S., 278 White, R.C., 161 Whitecar, C.K., 240 Whitehouse, D.G., 117 Whitten, D.G., 314 Whittingham, S., 360 Whitwood, A.C., 272 Wiberg, K.B., 391 Widmer, J., 288 Widom, B., 30 Wiel, J.A., 91 Wiel ter, M.K.J., 443 Wielgus, I., 50 Wienk, M.M., 43, 50 Wiesemann, T.L., 314 Wiest, O., 193, 323, 327, 363, 365 Wilbrandt, R., 335 Wilham, A.L., 310 Wilhelm, H., 424 Wilkins, R.G., 61, 62 Wilkinson, G., 59, 69 Will, S., 30 Willbrandt, R., 183, 335 Wille, U., 63, 193 Willhalm, B., 16, 353 Williams, F., 8, 129, 130, 339, 362 Williams, J.M., 416 Willner, I., 278 Wilson, G.S., 158 Wilson, I., 115 Wilson, S.R., 159 Wilson, W.R., 193 Windolph, C., 243 Winstein, S., 168 Winter, R.F., 10 Wirth, D.D., 363 Wirz, J., 130 Wisniowski, P., 161 Wistrand, L.-G., 91 Witcomb, M.J., 240, 241 Wittingham, S., 360 Wittkop, P., 170 Woelfel, S., 71 Wolf, H.C., 417 Wolf, M.O., 15, 106 Wolfe, J.F., 7, 223, 231, 373, 391, 393 Wolin, M.S., 259 Wong, J.W., 391 CRC_9068_authorind.indd 468 Author Index Woods, H.J., 68 Woods, J.E., 302, 406 Woolley, H.W., 332 Wooster, C.B., 354 Worell, C.W., 185 Workentin, M.S., 146, 195, 298, 404 Wosinska, Z.M., 27 Wren, B.W., 129 Wright, G.J., 253 Wu, D., 86 Wu, L., 365 Wu, L.-M., 122, 231 Wu, P., 413 Wudl, F., 20, 420, 422 Wuethwein, E.-U., 69 Wurche, F., 344 Wurst, K., 35, 37 Wurz, P., 416 Wyatt, P.B., 20 X Xia, Sh., 229 Xi’an, S., 55 Xiao, H.-Y., 332 Xie, Z., 416 Xiong, F., 282 Xu, H., 331 Xu, L., 296 Xu, Q., 253, 255 Y Yabe, M., 408 Yacovan, A., 73 Yagubskii, E.B., 410, 414, 417 Yagyu, T., 42 Yakiyama, Y., 410 Yakovleva, E.A., 86 Yakuphanoglu, F., 50 Yakushi, K., 411 Yamabe, T., 178 Yamada, H., 57 Yamada, M., 300 Yamaguchi, J., 183 Yamaguchi, K., 261 Yamaguchi, T., 416 Yamaguchi, Y., 110, 253, 255, 285 Yamaji, K., 414 Yamamoto, H., 56, 273 Yamamoto, K., 2, 91, 358, 416 Yamamoto, S., 273 Yamamura, H., 91 Yamashiro, D., 382 Yamanaka, S., 412 Yamashita, T., 52 Yamashita, Y., 411 Yamataka, H., 119, 122 Yamawaki, K., 392 Yamazaki, D., 336 Yamazaki, I., 190 Yamochi, H., 410 Yan, H., 51 Yan, J., 305 Yan, X.Z., 50 Yanagida, N., 127 Yanejida, S., 312 Yang, A., 87 Yang, D.-L., 231 Yang, G., 282 Yang, J., 34, 173, 365, 370 Yang, L., 124, 365 Yanilkin, V.V., Yano, M., 43, 44, 232 Yanovsky, A.I., 97 Yao, T., 148, 149 Yao, Y.M., 87 Yarkov, S.P., 230 Yarovoy, K.A., 256 Yashiro, H., 161 Yasinskii, O.A., 381 Yasuhara, A., 94 Yasui, Sh., 12, 118 Yasuoka, N., 413 Yasupka, N., 413 Yates, B.F., 161, 163 Yates, P., 369 Yeh, S.-R., 175, 193 Yff, D., Yin, Y., 257 Yip, S., 52 Yitzchaik, S., 240 Yonekuta, Y., 52 Yonezawa, T., 149 Yoon, K., 131, 291 Yoshida, H., 53 Yoshida, K., 419 Yoshida, Y., 52, 53, 326 Yoshida, Z.-i., 110 Yoshifuji, M., 13, 14 Yoshihara, K., 301 Yoshikava, K., Yoshikawa, K., 190 Yoshimura, M., 239 Yoshinary, Y., 359 Yoshino, K., 240 Yoshiura, N., 87 You, M.L., 87, 351 Younathan, J., 271 Young, J., 63 Young, R.D., 34 Youngman, R.J., 195 Youngs, W.J., 372 Yu, A., 27 Yu, H.-Zh., 37 Yu, T.J., 87 Yu, Y., 298 Yuan, L., 135 Yuang, P., 404 Yuasa, J., 370 Yueh, W., 110, 360, 361, 366 Yumura, M., 238 Yun, B.-S., 227 Yurchenko, A.G., 262 Yurkovskaya, A.V., 161 9/4/2008 11:45:50 AM Author Index Yur’ev, V.P., 94 Yus, M., 87 Yusupov, R.G., 120 Yuzhalkin, V.N., 27 Z Zabel, M., 10 Zagorska, M., 50 Zagorski, M.G., 340 Zagumennov, V.A., 152 Zahnow, E.W., 105, 106 Zahurak, S.M., 416 Zaikov, G.E., 58 Zakrewski, J., 37 Zaleski, J.M., 35 Zalis, S., 10, 179 Zanardi, Ch., 336 Zanello, P., 37 Zang, J., 434 Zanirato, P., 335 Zapol’skikh, V.V., 63 Zaripov, R.N., 63 Zavalij, P.Y., 360 Zavaliy, I.Yu., 360 Zelechonok, Yu.B., Zentel, R., 443 Zerbetto, F., 301 Zerner, M.C., 249, 253 CRC_9068_authorind.indd 469 469 Zgierski, M.Z., 52 Zhang, B., 282 Zhang, G., 2, 4, 282 Zhang, F.S., 404 Zhang, H., 60 Zhang, J., 383 Zhang, K.-D., 231 Zhang, R., Zhang, Sh., 34 Zhang, W., 365 Zhang, X.-M., 21, 231 Zhang, Y., 135, 296, 386 Zhang, Z., 34 Zhao, B.-J., 290 Zhao, F.Q., 404 Zhao, C.-X., 25 Zhao, G., 365 Zhao, J., 166, 286 Zhao, Y., 20–22, 29 Zhdanov, S.I., 3, 4, 177 Zheng, G.Z., 73 Zheng, X., 249, 253 Zheng, Z., 286 Zheng, Z.-R., 40, 206 Zhi, J.F., 405 Zhilyaeva, E.I., 409, 414–416 Zhil’tsov, V.V., 34 Zhou, D., 28 Zhou, J., 91 Zhou, Sh.-Q., 19 Zhou, Y., 365 Zhou, X.H., 404 Zhu, Z., 183 Zhu, Zh., 130 Zhumagaliev, A.S., 434 Zhumagaliev, S.Zh., 434 Ziegler, T., Zielinski, P.A., 27, 300 Zielonka, J., 127, 385 Ziessel, R., 297 Zimmerman, H.E., 354, 356 Zink, J.I., 340 Ziolkovskiy, D.V., 418 Zlotskii, S.S., 5, 129, 209, 325 Zoebisch, E.G., 256 Zojer, E., 42 Zollinger, H., 67, 236 Zoltewicz, J.A., 287 Zona, T.A., 363 Zorin, V.V., 5, 129, 209, 325 Zorina, L.V., 410, 414 Zotti, G., 52 Zubarev, R.A., 165 Zuccala, A., 442 Zugaro, L.M., 375 Zuilhof, H., 120, 123 Zuman, P., 229 Zverev, V.V., 167 Zwier, J., 157 Zweier, J.L., 183, 229 9/4/2008 11:45:51 AM CRC_9068_authorind.indd 470 9/4/2008 11:45:51 AM Subject Index A Acidity of organic anion-radicals, 19, 21–22 of organic cation-radicals, 22–29, 379–387 Acyloxylation oxidative, 108–110 Allenes ion-radicals of, 14, 185, 354 Anion-radicals acidity of, see Acidity basicity of, see Basicity confined, 135 definition of, 1, 112, 125 in ambient atmosphere, 72, 88 in water solutions, 48–49, 72, 88 Antiferromagnetism in organic ion-radical treaties, 42, 46, 48, 50, 89, 420, 423 Antimony chlorides as one-electron oxidants, 68–69, 91, 112–113, 185 Aromatization in organic ion-radicals, 30, 163, 343, 385, 414 Atropoisomerism in ion-radicals, 152, 183–184, 332 Azoxy compounds ion-radical reactions of, 100–101 B Barbier reaction ion-radical mechanism of, 330 Basicity of organic anion-radicals, 16–20 of organic cation-radicals, 29–30 Benzynes anion-radicals of, 164–165 Binaphthyls anion-radicals of, 152, 183–185, 332 cation-radicals of, 254 Biomedical activity ion-radical aspects of, 24, 57, 60–62, 94, 115–118, 126, 130–131, 161, 186–196, 249, 259, 274, 278, 340, 373, 387, 431–433 Birch reaction ion-radical mechanism of, 89, 124, 354–356 Biphenyls chloro-, anion-radicals of, 94 Bonds dangling, 363, 364 odd-electron multi-centered, 7, 27, 156–161, 165, 219, 299, 339–340 Boron-containing organic ion-radicals, 12, 40, 155, 156, 179, 180 Bouveault-Blanc reaction ion-radical mechanism of, 16–17, 308, 352–353 Butadienes anion-radicals, 174–175 cation-radicals, 178, 363–365 C Carbenoids ion-radicals of, 35, 92, 129, 307 Carbonate radical of, 60–61 Carotenoids ion-radicals of, 23–24, 337–338 Cation-radicals acidity of, see Acidity basicity of, see Basicity confined, 28, 130–135 definition of, 1, 112 in ambient atmosphere, 91 on catalytic surfaces, 28, 59 Cerium ammonium nitrate as one-electron oxidant, 118, 279, 382–383 Chalcogen-containing organic ion-radicals 144–146, 153, 157–161, 207, 274–276, 279, 295–297, 299, 333–334, 387, 395–397, 409–413, 434 Chalcogenadiazole in ion-radical treaties, 4, 8, 20, 31 Chalcogenides as one-electron oxidants, 273 organic as one-electron reductants, 209–210, 273, 324, 375–376 Charge transfer, 29, 38–39, 52, 72, 95, 130, 135, 307, 314, 316 Chelation by organic ion-radicals of metallic cations, 4–5, 34, 112, 169, 171–173, 176–178, 327 of protons, 99, 175–176, 356 Cleavage in ion-radicals concerted, 1, 208, 398 mesolytic, 143, 385 pi-catalysis of, 393, 394 stepwise, 1, 144, 208, 427 Conductivity electric, in organic ion-radical treaties, 49–50, 151, 359, 409–420, 423–424 Corrols cation-radical basicity, 29–30 Cresol ortho-, intramolecular hydrogen bonding in cation-radical of, 379, 380 Cucurbituriles hosts for ion–radical guests, 133–135 CWRD (Cold Window Radical Discharge), 128 471 CRC_9068_SUBJECTIND.indd 471 9/4/2008 11:42:07 AM 472 Cyclodextrins hosts for ion-radical guests, 133–135 Cyclooctatetraene excess-electron forms, 9, 41, 70, 93, 98, 100–102, 104, 107, 123, 168, 324 D Dehalogenation reductive, 8–9, 94, 207–210, 214–215 Delignification of wood pulp, in organic ion-radical treaties, 61, 428–433 Dendrimers in ion-radical states, 48–51 Deprotection of functional groups, ion-radical approaches, 273, 382–384 Desulfurization of fuels, in organic ion-radical treaties, 434–435 Diazonium ions in redox reactions, 4–5, 60, 163–164, 177–178, 215, 262–263, 359, 371, 389 Diels–Alder reaction ion-radical initiation of, 110, 135, 362–367, 369–370 Dimerization with organic ion-radical participation, 94, 112, 133, 150–152, 207, 353, 391 DNA ion-radical repair of, 191–194 E Ecology ion-radical aspects of, 61–62, 117, 195–196, 260, 307, 340, 433–435 Effects in ion-radical organic chemistry acoustic-field, 87, 279–281, 285, 330, 351, 354, 368–369, 417 aggregation, 89, 110–114, 233–234 alpha, 25, 27, 56, 92, 159, 330 beta, 25 bridge, 10–16, 36–38 cage-solvent, 149, 224, 232, 242, 257, 262, 273, 278, 295, 302, 310–312, 397–398 confinement, 28–29, 58 electric-field, 67, 274–278 electron-memory, 403–405 element, 410–413, 424 fastener, 413 Hall’s, 420–421 in capsules, 133–135, 190 in micelles, 130, 131, 255–256, 278, 302 in porous catalysts, 28–29, 131–133, 256 in zeolites/molecular ion-pairing, 5, 14, 18, 40, 47, 79, 86, 121, 306 isotope, 30, 117–126, 216–217, 242–243, 250 Jahn-Teller’s, 14, 41, 185, 235 CRC_9068_SUBJECTIND.indd 472 Subject Index Kramer’s (electron-emission), 283–284, 424–428 leaving-group, 144, 146, 210, 215–216, 247, 303, 391, 393–394, 396 light-irradiation, 66, 85, 94, 126, 271–274 magnetic-field, 277–278 mechanical-action, 281–286 meta, 43–46, 181–182 microwave, 87, 278–279, 384 ortho, 327 Peierls’, 413 polarity-solvent, 24, 208, 249–250, 294–297, 303–306 pressure–solvent, 304 proximity, 25, 41, 132 salt, 294–295, 308–316 sieves, 28, 131–133, 256–257, 337 size, 102–103, 168, 172, 175 solvent-polarity, 395 solvent–reorganization, 66–69, 111, 120, 207 solvent-viscosity, 278, 304, 307 steric, 25–28, 47–48, 56, 58, 106–110, 132–135, 144–145, 152–155, 160, 171–176, 183–185, 242, 280, 300, 310, 323–344, 364–366, 378, 385, 393–394, 405, 414–415 template, 100–103 Electrides, 86, 87 Electrocrystallization of organic ion-radical salts, 410, 417–420 Electrodes reactions upon, in relation to transformations in solution pool, 64–65, 67, 85, 95–115 surface control over reactivity of organic ion–radicals, 67, 95–96, 103–106 Electromers of ion–radicals, see also Luminomers and Somomers, 9–10, 13, 115, 232, 323 Electron transfer back, 126–127, 130, 132 catalysis, 31, 63, 71–72, 94, 216, 263, 274–277, 293–295, 378–379, 433 catalysis interphase, 395 dissociative, 7–8, 25, 60, 105 concerted, 7, 25, 96, 105, 119, 397–398 proton-coupled, 25, 96, 131, 380 stepwise, 8, 105, 222–223, 397–398 sticky-dissociative, 302–303 equilibrium of, 91, 93–94 intermolecular, 10–16, 361 intramolecular, 155, 180–183, 340, 361, 377, 393 through-bond, 10–12, 183, 340 through-space, 155, 183 Emeraldines, see Polyanilines ion-radicals of Encounter complexes in ion-radical organic reactions, 95, 218, 250, 252, 257, 259, 307, 316 Entrainment of ion-radical organic reactions, by chemical additives, 286–295 9/4/2008 11:42:08 AM Subject Index F Ferrimagnetism in organic ion-radical treaties, 421 Ferrocene derivatives anion-radicals of, 93, 146–147, 337 cation-radicals of, 34–37, 406–407, 421, 337 Ferromagnetism in organic ion-radical treaties, 43, 46–47, 50–52, 180–181, 420 Foerster cycle, 272 Franck-Condon principle, 301, 323 Fullerenes inside-cage electron movement, 415–416, 422, 358–359 ion-radicals of, 19, 30, 135, 147, 148, 151 H Housanes ion-radicals of, 183, 344 HSAB (Hard-Soft Acid Base) principle its applications to ion-radical organic reaction, 273, 309 Hund’s rule, see also Spin multiplicity, 420 Hydrogen bonds with participation of anion-radicals, 8, 36, 89, 175–176, 296, 298, 300, 302 cation-radicals, 36, 151, 296–298, 300, 302, 341, 380, 406, 410 Hydroxide ion in ion-radical organic reactions, 65–66, 218, 225 Hydroxyl radical its participation in chemical and biochemical transformations, 59, 62, 65–66, 218, 230, 244–245, 259, 425 Hydroxylation ion-radical mechanism of, 61–65, 204, 218, 235, 381 I Inhibitor method in diagnostics of ion-radical organic reactions, 205, 209, 224–226, 279 Iodination ion-radical mechanism of, 298, 311 Iodine reagents in ion-radical organic reactions, 90, 281, 311, 368, 418 Ion pairs, 55, 85, 88, 111, 123, 168–178, 306, 308–313 Ion-radicals organic distonic, 13, 26, 143, 154, 195, 300, 344 distonoid, 167–168, 388 nonclassic, 29, 153–154, 161 CRC_9068_SUBJECTIND.indd 473 473 Ionic liquids as mediums in ion-radical organic reactions, 50, 279, 307–308, 363 Isotope enrichment of organic products, ion-radical method, 30, 120–125, 127 K Kagan reactant, see Samarium diiodide Kolbe reaction, 64–65, 90 L LFER (Linear free energy relationship) in ion-radical organic reactions, 3–4, 7, 14, 16, 71, 213, 259, 366 Lignan its ion-radical chemistry, 24, 433–434 Lignin its ion-radical chemistry, 24, 429–433 Liquid crystals as mediums in ion-radical organic reactions, 306–307 Locaslization length (LL), 52–53 Lubricity ion-radical mechanism of, 424–428 Luminiomers, see Electromers and Somomers, 9–10, 13, 115 M Magic Blue, see also Trisarylamine cation-radicals, 67–68, 344 Magic Green, see also Trisarylamine cation-radicals, 67–68 Marcus theory Marcus, Hush, Sutin approach, 213 of electron transfer, 301–302, 316 Matrix isolation of organic ion-radicals, 126–130, 163–164 Mediators in ion-radical organic reactions, 93, 276–277 Meerwein reaction ion-radical mechanism of, 262–263 Meerwein’s salts in one-electron oxidation, 69 Metallocomplexes anion-radicals of, 30–33, 72, 88–89, 93, 146–148, 313, 338, 350–351 cation-radicals of, 36–39, 312, 406, 421–423 Metamagnetism in organic ion-radical treaties, 421 Microelectromechanics, see also Nanoelectromechanics, 443 9/4/2008 11:42:08 AM 474 Subject Index N R Nanodots their generation in ion-radical reactions, 418 Nanoparticals their generation in ion-radical reactions, 131, 237–238, 241 Nanoelectromechanics, see Microelectromechanics, 443 Nitration ion-radical mechanism of, 247–262 Nitronium as participant of ion-radical organic reactions, 66–67, 247–252, 260–261 Nitrosonium as participant of ion-radical organic reactions, 66–67, 251–254, 258–260 Nitroxide-containing ion-radicals, 41–42 Radical/spin traps, see Spin/radical traps Reorganization energy in ion-radical organic reactions, 251, 260, 301–303, 307, 339 Robin-Day classification of redox centers in organic molecules, 10, 34–35, 37, 41 Rose Bengal, 403–404 Rotation around bonds in organic ion-radicals, 263–277, 294–295, 327, 331, 333–338, 350–352, 365, 378 O Oligothiophenes ion-radicals of, 133, 151 Orbital control, frontier, over electronic structure of organic ion-radicals, 3–6, 12, 144–153, 182, 185, 261, 410 Oxygen atomic, anion-radical of, 58 molecular, anion-radical, see also Superoxide ion, 54–59, 71, 117, 159, 243–244, 298–294, 356 cation-radical, 58–59 Ozone as participant of ion-radical organic reactions, 57 P Paramagnetism in organic ion-radical treaties, 42, 420, 423 Phase transition liquid-to-solid, in preparation of organic metals, 418 Phosphorus-containing organic ion-radicals, 145, 150, 152–153 Photoinitiation of ion-radical organic reactions, 52 Polyanilines ion-radicals of, 50, 136, 359–360 Poly(ion-radicals), 37, 39–48 meta-phenylene linker approach to, 43–46, 50–51, 178–181 “metal radical” approach to, 413 spin alignment in, 39–48, 50–52 Polymerization ion-radical mechanism of, 358–362, 426 Polymers ion-radicals of, 48–53 Polysilane ion-radicals of, see Silicon-containing ion radicals, 52–53 Polythiophenes ion-radicals of, 51–52 CRC_9068_SUBJECTIND.indd 474 S Samarium diiodide as one-electron reductant, see also Kagan reagent, 72–73, 90, 370, 378, 395 Sandmeyer reaction cation-radical mechanism of, 262–263 Scattering of spin and charge, see Distonic ion-radicals Silicon-containing ion-radicals, 52–53, 408 Solid-state reactions in org ion-radical treaties, 126–130, 281–286, 377, 409–428 Solvation in organic ion-radical treaties, 8, 25, 66, 85, 119–120 Somomers of organic ion-radicals, see also Electromers or Luminomers, 9, 10, 13, 115, 232, 323 Spin glasses, 232, 422–423 multiplicity, see also Hund’s rule, 420 Spin/radical trap method in diagnoistics of ion-radical organic reactions, 68, 227–232 Stilbenes ion-radical chemistry of, 14–16, 34, 47–48, 57, 94, 96–98, 106–110, 146, 154–155, 169–170, 181, 277–278, 293–295, 297, 349–350, 377, 403–404, 430 Substitution electrophilic, ion-radical mechanism of, 4–5, 247–262 ion-radical, in connection with polar mechanism of, 247–262, 391 nucleophilic, ion-radical mechanism of, 7–8, 65–66, 323, 397, 398 radical nucleophilic (SRN), 65, 209–210, 222–223, 243–244, 275–277, 281, 323, 373–376, 391–398 vicarious, 150 Sulfate radical of, 62–65 upon zirconia surface, 63–64 Sulfite radical of, 61–62 9/4/2008 11:42:08 AM Subject Index Sulfur dioxide anion radical of, Superoxide ion, see Oxygen molecular, anion-radical of Synthons ion-radical routes to, 387–388 T ter Meer reaction ion-radical mechanism of, 243–247 Tetrathiafulvalene cation-radical of as a trigger, 148, 296–299, 371, 388–390, 406 in dendrimers, 131 in organic conductors, 410–416 in organic magnets, 423 Thianthrene cation radical of, 43, 67, 124, 133, 178, 289–291, 337 CRC_9068_SUBJECTIND.indd 475 475 Transition metal ions as one-electron oxidants, 69–73 Trisarylamine cation radicals of, 67–68, 182, 344, 352, 359–361, 365, 367, 378–379, 383, 387 V Valence shell, expansion of in organic ion-radicals, 8, 33, 156 Variamine Blue cation-radical route to formation of, 114 Viologens cation-radicals of, 90, 92, 98, 118, 133, 135, 316 W Wuerster Blue, 178–179 Wuerster’s salts, 178–179, 327 9/4/2008 11:42:09 AM CRC_9068_SUBJECTIND.indd 476 9/4/2008 11:42:09 AM ... an overview of organic ion-radical reactions and explains the principles of the ion-radical organic chemistry Methods of determining ion-radical mechanisms and controlling ion-radical reactions... Mes∗=C6H2-t-Bu 3-2 ,4,6 SCHEME 1.6 Ar P= C +e Ar P C Ar P − Ar=C6H2-t-Bu 3-2 ,4,6 SCHEME 1.7 CRC_9068_Ch001.indd 13 9/8/2008 6:08:39 PM 14 Ion-Radical Organic Chemistry: Principles and Applications. .. between 1,4-dimethoxybenzene and 7,7-dicyanobenzoquinone methide moieties CRC_9068_Ch001.indd 11 9/8/2008 6:08:38 PM 12 Ion-Radical Organic Chemistry: Principles and Applications in syn- or anti-cyclophane